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In the title mol­ecule, C15H14N2OS, the seven-membered ring adopts a boat conformation. The carbonyl, imine and phenyl groups lie to one side of the mol­ecule, and the thienyl ring and methyl­ene group to the other.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801004585/ci6018sup1.cif
Contains datablocks general, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801004585/ci6018Isup2.hkl
Contains datablock I

CCDC reference: 162824

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.045
  • wR factor = 0.152
  • Data-to-parameter ratio = 17.7

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry




Comment top

Compounds related to the title compound, (I), are known to enhance agonist binding to the A1 adenosine receptor (Tranberg et al., 2001). In this context, the conformation of the seven-membered ring is of some interest as this determines the conformation of the N atoms which, in turn, influences activity.

The structure of (I) is shown in Fig. 1 from which it can be seen that the seven-membered ring adopts a boat conformation. In this description, the N1, N4, C2 and C5 atoms are essentially coplanar, so that the N1—H, C2O2 and phenyl groups lie to one side of the molecule, and the thienyl ring and methylene group to the other. Centrosymmetrically related pairs of molecules associate via hydrogen bonding between the amide groups: N1—H1 0.88 Å, H1···O2i 1.95 Å, N1···O2i 2.824 (3) Å and N1—H1···O2i 173° [symmetry code: (i) 2 - x, -y, -z]. Interactions of the type C—H···π also operate in the structure such that C3—H3b···Cgii is 2.62 Å (Cg is the centroid of the thienyl ring), with the angle subtended at H3b being 162° [symmetry code: (ii) x, 1/2 - y, -1/2 + z].

Experimental top

Dry ammonia gas was introduced with ice cooling, to a solution of N-(3-benzoyl-4,5-dimethyl-thiophen-2-yl)-2-iodoacetamide (3.2 g, 8.0 mmol) in CHCl3 (dry, 10 ml) and methanol (dry, 1 ml) over a period of 40 min. The mixture was then stirred at room temperature for a further 5 h. After this time, ice and water were added. The organic phase was washed with NaHCO3 solution (saturated, 10 ml), H2O (3 × 10 ml) and dried with MgSO4. Subsequent removal of solvent under reduced pressure gave 2.024 g of crude product which was purified with silica chromatography. Hexane–ethyl acetate (1:1) as eluent gave the product (1.158 g, 53%) which was recrystallized from ethyl acetate to give clear crystals, m.p. (decomposition) 511–514 K. 1H NMR (DMSO-d6) δ 1.50 (s, 3H, CH3), 2.24 (s, 3H, CH3), 3.80 (d, 1H, CH2), 4.50 (d, 1H, CH2), 7.39–7.45 (m, 5H, C6H5), 11.03 (br, s, 1H, NH). 13C NMR (DMSO-d6) δ 12.43, 14.09, 57.85, 125.02, 125.94, 128.26, 128.34, 128.98, 129.93, 138.48, 142.48, 166.36, 168.29.

Computing details top

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1996); data reduction: TEXSAN (Molecular Structure Corporation, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The molecular structure and crystallographic numbering scheme for (I). Displacement ellipsoids are shown at the 50% probability level (ORTEPII; Johnson, 1976).
(I) top
Crystal data top
C15H14N2OSDx = 1.348 Mg m3
Mr = 270.34Mo Kα radiation, λ = 0.7107 Å
Orthorhombic, PbcaCell parameters from 24 reflections
a = 34.115 (6) Åθ = 7.4–10.3°
b = 10.4377 (17) ŵ = 0.24 mm1
c = 7.484 (3) ÅT = 173 K
V = 2664.7 (13) Å3Block, colourless
Z = 80.50 × 0.31 × 0.18 mm
F(000) = 1136
Data collection top
Rigaku AFC-7R
diffractometer
Rint = 0.030
Radiation source: rotating anodeθmax = 27.5°, θmin = 3.1°
Graphite monochromatorh = 044
ω scansk = 1310
5860 measured reflectionsl = 89
3057 independent reflections3 standard reflections every 400 reflections
2084 reflections with I > 2σ(I) intensity decay: 0.6%
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.152H-atom parameters constrained
S = 1.02 w = 1/[σ2(Fo2) + (0.1P)2]
where P = (Fo2 + 2Fc2)/3
3057 reflections(Δ/σ)max = 0.002
173 parametersΔρmax = 0.40 e Å3
0 restraintsΔρmin = 0.25 e Å3
Crystal data top
C15H14N2OSV = 2664.7 (13) Å3
Mr = 270.34Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 34.115 (6) ŵ = 0.24 mm1
b = 10.4377 (17) ÅT = 173 K
c = 7.484 (3) Å0.50 × 0.31 × 0.18 mm
Data collection top
Rigaku AFC-7R
diffractometer
Rint = 0.030
5860 measured reflections3 standard reflections every 400 reflections
3057 independent reflections intensity decay: 0.6%
2084 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0450 restraints
wR(F2) = 0.152H-atom parameters constrained
S = 1.02Δρmax = 0.40 e Å3
3057 reflectionsΔρmin = 0.25 e Å3
173 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S80.955883 (15)0.08457 (5)0.50528 (7)0.02942 (18)
O20.98056 (5)0.15129 (16)0.0480 (2)0.0359 (4)
N10.96128 (5)0.01871 (17)0.1742 (2)0.0279 (4)
H10.97900.03830.14230.084 (3)*
N40.88856 (5)0.16611 (18)0.0892 (2)0.0290 (4)
C20.95891 (6)0.1303 (2)0.0795 (3)0.0280 (5)
C30.92695 (6)0.2212 (2)0.1387 (3)0.0293 (5)
H3a0.92830.23380.26970.084 (3)*
H3b0.93040.30540.08010.084 (3)*
C8a0.93706 (6)0.0093 (2)0.3191 (3)0.0254 (4)
C5a0.89758 (6)0.01687 (19)0.3362 (3)0.0260 (4)
C50.87560 (6)0.0755 (2)0.1876 (3)0.0279 (5)
C6'0.84207 (7)0.0070 (3)0.5753 (4)0.0418 (6)
H6a0.82690.04770.47950.084 (3)*
H6b0.84370.06530.67770.084 (3)*
H6c0.82910.07250.61190.084 (3)*
C60.88275 (6)0.0227 (2)0.5089 (3)0.0284 (5)
C70.91090 (7)0.0793 (2)0.6114 (3)0.0293 (5)
C7'0.90801 (8)0.1298 (3)0.7991 (3)0.0422 (6)
H7a0.93340.16540.83530.084 (3)*
H7b0.88800.19700.80420.084 (3)*
H7c0.90080.05990.88010.084 (3)*
C510.83687 (6)0.0197 (2)0.1352 (3)0.0313 (5)
C520.82830 (7)0.1093 (2)0.1632 (4)0.0411 (6)
H520.84640.16180.22560.084 (3)*
C530.79324 (7)0.1622 (3)0.1004 (4)0.0499 (7)
H530.78770.25030.11980.084 (3)*
C540.76674 (7)0.0859 (3)0.0099 (4)0.0521 (8)
H540.74300.12180.03380.084 (3)*
C550.77466 (7)0.0421 (3)0.0170 (4)0.0497 (7)
H550.75620.09430.07840.084 (3)*
C560.80937 (7)0.0953 (3)0.0451 (3)0.0403 (6)
H560.81450.18370.02640.084 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S80.0274 (3)0.0309 (3)0.0300 (3)0.0002 (2)0.0057 (2)0.0043 (2)
O20.0311 (9)0.0408 (9)0.0357 (8)0.0024 (7)0.0054 (7)0.0082 (7)
N10.0240 (8)0.0309 (10)0.0288 (9)0.0015 (7)0.0010 (7)0.0015 (7)
N40.0264 (9)0.0321 (9)0.0285 (9)0.0079 (7)0.0015 (7)0.0015 (8)
C20.0249 (10)0.0310 (11)0.0281 (11)0.0032 (8)0.0045 (8)0.0016 (9)
C30.0313 (10)0.0293 (11)0.0272 (10)0.0010 (8)0.0013 (9)0.0007 (9)
C8a0.0253 (10)0.0267 (10)0.0242 (10)0.0008 (8)0.0029 (8)0.0002 (8)
C5a0.0235 (10)0.0267 (10)0.0278 (11)0.0004 (8)0.0020 (8)0.0023 (8)
C50.0240 (10)0.0313 (11)0.0282 (10)0.0054 (8)0.0011 (8)0.0048 (9)
C6'0.0337 (13)0.0490 (15)0.0428 (14)0.0034 (11)0.0132 (11)0.0033 (11)
C60.0274 (10)0.0279 (11)0.0301 (11)0.0021 (8)0.0017 (9)0.0022 (9)
C70.0329 (11)0.0273 (11)0.0276 (10)0.0027 (8)0.0008 (9)0.0009 (9)
C7'0.0529 (15)0.0424 (14)0.0314 (12)0.0053 (11)0.0006 (11)0.0053 (11)
C510.0230 (10)0.0409 (13)0.0300 (11)0.0059 (9)0.0024 (9)0.0060 (10)
C520.0270 (11)0.0450 (14)0.0514 (15)0.0018 (10)0.0066 (11)0.0059 (12)
C530.0313 (13)0.0495 (15)0.0689 (19)0.0031 (11)0.0019 (13)0.0134 (14)
C540.0241 (11)0.073 (2)0.0591 (18)0.0003 (12)0.0074 (11)0.0219 (16)
C550.0277 (12)0.0731 (19)0.0483 (16)0.0124 (12)0.0074 (11)0.0052 (15)
C560.0296 (12)0.0479 (15)0.0433 (13)0.0099 (10)0.0061 (10)0.0046 (11)
Geometric parameters (Å, º) top
S8—C8a1.723 (2)C5—C511.496 (3)
S8—C71.729 (2)C6'—C61.506 (3)
O2—C21.227 (3)C6—C71.364 (3)
N1—C21.365 (3)C7—C7'1.503 (3)
N1—C8a1.394 (3)C51—C521.394 (3)
N4—C51.278 (3)C51—C561.398 (3)
N4—C31.477 (3)C52—C531.399 (3)
C2—C31.512 (3)C53—C541.382 (4)
C8a—C5a1.380 (3)C54—C551.378 (5)
C5a—C61.448 (3)C55—C561.388 (4)
C5a—C51.474 (3)
C8a—S8—C791.50 (11)C5a—C5—C51119.06 (18)
C2—N1—C8a123.19 (18)C7—C6—C5a112.32 (19)
C5—N4—C3116.76 (17)C7—C6—C6'123.6 (2)
O2—C2—N1121.4 (2)C5a—C6—C6'123.9 (2)
O2—C2—C3123.4 (2)C6—C7—C7'129.1 (2)
N1—C2—C3115.20 (18)C6—C7—S8112.36 (17)
N4—C3—C2108.75 (17)C7'—C7—S8118.45 (18)
C5a—C8a—N1127.48 (19)C52—C51—C56118.4 (2)
C5a—C8a—S8112.28 (16)C52—C51—C5121.44 (19)
N1—C8a—S8120.23 (15)C56—C51—C5120.0 (2)
C8a—C5a—C6111.51 (19)C51—C52—C53120.7 (2)
C8a—C5a—C5120.59 (19)C54—C53—C52119.8 (3)
C6—C5a—C5127.88 (19)C55—C54—C53120.1 (2)
N4—C5—C5a124.46 (19)C54—C55—C56120.4 (3)
N4—C5—C51116.26 (19)C51—C56—C55120.6 (3)

Experimental details

Crystal data
Chemical formulaC15H14N2OS
Mr270.34
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)173
a, b, c (Å)34.115 (6), 10.4377 (17), 7.484 (3)
V3)2664.7 (13)
Z8
Radiation typeMo Kα
µ (mm1)0.24
Crystal size (mm)0.50 × 0.31 × 0.18
Data collection
DiffractometerRigaku AFC-7R
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
5860, 3057, 2084
Rint0.030
(sin θ/λ)max1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.045, 0.152, 1.02
No. of reflections3057
No. of parameters173
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.40, 0.25

Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1996), TEXSAN (Molecular Structure Corporation, 1997), SIR97 (Altomare et al., 1997), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), SHELXL97.

 

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